Stereoselective total synthesis of 10-epi-tirandamycin E

Engineering P450 TamI as an Iterative Biocatalyst for Selective Late-Stage C–H Functionalization and Epoxidation of Tirandamycin Antibiotics

“…anthracis 34f2 and S. pneumoniae ATCC 49619 compared to the other newly characterized congeners, is readily obtained by epoxidation and C18 methyl oxidation, whereas these oxidative decorations would normally be challenging to access in a direct fashion without competing oxidation of the existing methylene units in the substrate structure. − Our work also illustrates that TamI can be manipulated to effectively catalyze a four-step oxidative cascade without the assistance of the oxidative partner TamL, opening new avenues for the development of multifunctional oxidation catalysts with enhanced iterative properties. These results demonstrate the power of iterative bacterial P450s to develop new tools for selectivity and cascade reactions, expanding enzyme-controlled iterative C–H functionalization and epoxidation of complex scaffolds and streamlining the synthesis of high-value target compounds.…”

“…15,17 The promising biological activities and molecular complexity of tirandamycins has attracted considerable attention from synthetic chemists for the last 40 years. [23][24][25] Although notable routes have been developed for the racemic and enantioselective construction of this synthetic target, they rely on extensive functional group manipulation for introducing the oxygen atoms decorating the bicyclic moiety. Synthetic approaches often are designed for a specific member of this natural product group, with the oxidation level pre-defined at an early stage of the synthesis.…”

Studies toward the Synthesis of Colletotrichamide A: Construction of the C19–C30 Segment of the Molecule

“…Scheme 1: Retrosynthetic analysis Thus, as per the retrosynthetic plan, synthesis of vinyliodide 9 started with Maruoka-Keck 6 allylation reaction of known aldehyde 7 11, to furnish the desired homo allylic alcohol 14 (dr = 10:1) with 80% yield. TBS ether protection of compound 14 was carried out with tertbutyldimethylsilyl trifluoromethanesulfonate in presence of 2,6-lutidine to deliver the compound 15 with 90% yield.…”

Metathesis Reactions in Natural Product Fragments and Total Syntheses

“…These molecules are organized under various transformations in the following sequence: 1) ring‐closing metathesis, 2) cross metathesis, 3) ring‐closing alkyne metathesis, and 4) ring‐closing enyne metathesis. 1) Ring‐closing metathesis : kanamienamide ( 37 ), [100] (+)‐chinensiolide B ( 38 ), [101] BMS‐846372 ( 39 ), [102] daphniyunnine B core ( 40 ), [103] clavilactone D ( 41 ), [104] pechueloic acid ( 42 ), [105] (−)‐deoxoapodine ( 43 ), [106] zephyranthine ( 44 ), [107] palodesangrens core ( 45 ), [108] (−)‐stemaphylline ( 46 ), [109] pavidolide B ( 47 ), [110] 7‐deoxypancratistatin ( 48 ), [111] (+)‐4‐ ɑ ‐dehydroxycrinamabine ( 49 ), [112] (−)‐elymoclavine ( 50 ), [113] viridin ( 51 ), [114] (−)‐crinane ( 52 ), [112] conduramine B‐1( 53 ), [115] ellipticine quinone ( 54 ), [116] (−)‐tegafur ( 55 ), [117] tetraponerine ( 56 ), [118] (−)‐cermizine B ( 57 ), [119] (Figure 7) (±)‐lycojaponicm ( 58 ), [120] (−)‐zeylenol ( 59 ), [121] aphanamal ( 60 ), [122] (+)‐epiquinamide ( 61 ), [123] erythrinane core ( 62 ), [124] (−)‐pseudodistomin E ( 63 ), [125] toxicodenane A ( 64 ), [126] ipomoeassin F ( 65 ), [127] scholarisine K ( 66 ), [128] panal core ( 67 ), [129] (+)‐crotanecine ( 68 ), [130] gagunin E analogue ( 69 ), [131] R‐(−)‐ ɑ ‐cuparenone ( 70 ), [132] citreamicin‐η core ( 71 ), [133] brianthein A core ( 72 ), [134] (+)‐cryptoconcatone H ( 73 ), [135] neomarchantin A ( 74 ), [136] (+)‐methynolide ( 75 ), [137] 10‐epi‐tirandamycin ( 76 ), [138] greensporone C ( 77 ), [139] 5′‐hydroxy‐zearalenone ( 78 ), [140] cheloviolene A ( 79 ), [141] crassifoside F c...…”